Reversible hole engineering for single-wall carbon nanotubes

Experimental results are provided for reversible generation of holes on single-wall carbon nanotubes and their closing by temperature treatment. The generation of the holes was analyzed by checking the amount of C60 fullerenes that can be filled into the tubes and subsequently transformed to an inner-shell tube. The concentration of the latter was determined from the Raman response of the radial breathing mode. The tube opening process was performed by exposure of the tubes to air at elevated temperatures. This process was found to be independent from the tube diameters. In contrast, the tube closing process was found to depend strongly of the tube diameter. For large diameter tubes (d = 1.8 nm) the activation energy was 1.7 eV whereas for the small diameter tubes this energy was only 0.33 eV. Optimum conditions for tube closing were found to be one hour at 800 degrees C or 10 minutes at 1000 degrees C. From the almost identical Raman spectra for the tubes before and after engineering, a predominant generation of the holes at the tube ends is concluded.     

Noncovalent assembly of carbon nanotubes and single-stranded DNA: an effective sensing platform for probing biomolecular interactions

In this paper, we report the assembly of single-walled carbon nanotubes (SWNTs) and single-stranded DNA to develop a new class of fluorescent biosensors which are able to probe and recognize biomolecular interactions in a homogeneous format. This novel sensing platform consists of a structure formed by the interaction of SWNTs and dye-labeled DNA oligonucleotides such that the proximity of the nanotube to the dye effectively quenches the fluorescence in the absence of a target. Conversely, and very importantly, the competitive binding of a target DNA or protein with SWNTs for the oligonucleotide results in the restoration of fluorescence signal in increments relative to the fluorescence without a target. This signaling mechanism makes it possible to detect the target by fluorescence spectroscopy. In the present study, the schemes for such fluorescence changes were examined by fluorescence anisotropy and fluorescence intensity measurements for DNA hybridization and aptamer-protein interaction studies.     

DNA-decorated carbon nanotubes for chemical sensing

We demonstrate a new, versatile class of nanoscale chemical sensors based on single-stranded DNA (ss-DNA) as the chemical recognition site and single-walled carbon nanotube field effect transistors (swCN-FETs) as the electronic read-out component. swCN-FETs with a nanoscale coating of ss-DNA respond to gas odors that do not cause a detectable conductivity change in bare devices. Responses of ss-DNA/swCN-FETs differ in sign and magnitude for different gases and can be tuned by choosing the base sequence of the ss-DNA. ss-DNA/swCN-FET sensors detect a variety of odors, with rapid response and recovery times on the scale of seconds. The sensor surface is self-regenerating: samples maintain a constant response with no need for sensor refreshing through at least 50 gas exposure cycles. This remarkable set of attributes makes sensors based on ss-DNA decorated nanotubes very promising for "electronic nose" and "electronic tongue" applications ranging from homeland security to disease diagnosis.     

Reversible metal-insulator transitions in metallic single-walled carbon nanotubes

We report on reversible metal to insulator transitions in metallic single-walled carbon nanotube devices induced by repeated electron irradiation of a nanotube segment. The transition from a low-resistive, metallic state to a high-resistive, insulating state by 3 orders of magnitude was monitored by electron transport measurements. Application of a large voltage bias leads to a transition back to the original metallic state. Both states are stable in time, and transitions are fully reversible and reproducible. The data is evidence for a local perturbation of the nanotube electronic system by removable trapped charges in the underneath substrate and excludes structural damage of the nanotube. The result has implications for using electron-beam lithography in nanotube device fabrication.     

Cement-based sensors with carbon fibers and carbon nanotubes for piezoresistive sensing

Electrically conductive cementitious composites carrying carbon fibers and carbon nanotubes were developed and their ability to sense an applied compressive load through a measureable change in resistivity was investigated. Two types of cement-based sensors, one with carbon fibers alone and the other carrying a hybrid of both fibers and nanotubes, were considered. Direct comparisons were also made with traditional strain gauges mounted on the sensor specimens.Sensing experiments indicate that under cyclic loading, the changes in resistivity mimic both the changes in the applied load and the measured material strain with high fidelity for both sensor types. The response, however, is nonlinear and rate dependent. At an arbitrary loading rate, the hybrid sensor, containing a combination carbon fibers and nanotubes, produced the best results with better repeatability.     

Metal-decorated multi-wall carbon nanotubes for low temperature gas sensing

We investigate the possibility of using, as a gas sensitive material, multi-walled carbon nanotubes (MWCNT) covered with gold or silver nanoclusters deposited by thermal evaporation. Metal-decorated MWCNT were dispersed in an organic vehicle, micro-deposited onto silicon micro-machined sensor substrates and subsequently annealed to remove the organic vehicle. The resulting sensors are shown to be sensitive to NO₂ when operated at room temperature and significantly more selective than sensors based on MWCNT without metal nanoclusters attached to their surface.     

Optimized network of multi-walled carbon nanotubes for chemical sensing

This work reports the design of a resistive gas sensor based on 2D mats of multi-walled carbon nanotubes (MWCNTs) grown by aerosol-assisted chemical vapour deposition. The sensor sensitivity was optimized using chlorine as analyte by tuning both CNT network morphology and CNT electronic properties. Optimized devices, operating at room temperature, have been calibrated over a large range of concentration and are shown to be sensitive down to 27 ppb of chlorine. The as-grown MWCNT response is compared with responses of 2000?°C annealed CNTs, as well as of nitrogen-doped CNTs and CNTs functionalized with polyethyleneimine (PEI). Under chlorine exposure, the resistance decrease of as-grown and annealed CNTs is attributed to charge transfer from chlorine to CNTs and demonstrates their p-type semiconductor behaviour. XPS analysis of CNTs exposed to chlorine shows the presence of chloride species that confirms electron charge transfer from chlorine to CNTs. By contrast, the resistance of nitrogen-doped and PEI functionalized CNTs exposed to chlorine increases, in agreement with their n-type semiconductor nature. The best response is obtained using annealed CNTs and is attributed to their higher degree of crystallinity.     

Photoluminescence imaging of electronic-impurity-induced exciton quenching in single-walled carbon nanotubes

The electronic properties of single-walled carbon nanotubes can be altered by surface adsorption of electronic impurities or dopants. However, fully understanding the influence of these impurities is difficult because of the inherent complexity of the solution-based colloidal chemistry of nanotubes, and because of a lack of techniques for directly imaging dynamic processes involving these impurities. Here, we show that photoluminescence microscopy can be used to image exciton quenching in semiconducting single-walled carbon nanotubes during the early stages of chemical doping with two different species. The addition of AuCl(3) leads to localized exciton-quenching sites, which are attributed to a mid-gap electronic impurity level, and the adsorbed species are also found sometimes to be mobile on the surface of the nanotubes. The addition of H(2)O(2) leads to delocalized exciton-quenching hole states, which are responsible for long-range photoluminescence blinking, and are also mobile.     

Temperature sensing using individual single-walled carbon nanotubes

Molecular dynamics simulations and quantum transport theory are employed to study the temperature-dependent electrical properties of individual (12,0) zigzag and (5,5) armchair carbon nanotubes deposited on silicon substrates. The results demonstrate that the magnitude of the leakage current depends on the length of the nanotube. Furthermore, the leakage current is generated periodically along the length of the nanotube. Finally, the results indicate that given an appropriate value of the applied bias voltage, the induced current varies linearly with the temperature over specific temperature ranges. As a result, the temperature can be inversely derived from the measured current signal. Overall, the results show that the (12,0) zigzag and (5,5) armchair carbon nanotubes are suitable for temperature sensing applications over temperature ranges of 200-420?K and 300-440?K, respectively.     

Hydrogen sensing properties of multi-walled carbon nanotubes

The hydrogen sensing properties of multi-walled carbon nanotubes (MWNTs) synthesized by a hot filament CVD process are reported in this paper. The MWNTs were synthesized by a hot filament assisted chemical vapor deposition method using cobalt oxide nanoparticles as the catalyst on SiO₂ surfaces. The MWNTs were characterized with Raman spectroscopy and scanning electron microscopy. Two-terminal test devices were fabricated by depositing a layer of MWNTs between prefabricated gold electrodes on SiO₂ surfaces. The diameter of these MWNTs was in the 5–8 nm range. The sensitivity of carbon nanotubes was measured for different gas concentrations at different temperatures. It was found that the MWNTs were sensitive to H₂ in low temperature regions of 140–350 °C and had a maximum sensitivity (80%) at 230 °C. No sensitivity was observed at a temperature lower than 140 °C or higher than 400 °C. Though bare MWNTs are not sensitive to H₂ at room temperature, they exhibited very good sensing characteristics in the 140–300 °C range.     

Bright fluorescence from individual single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) have unique photophysical properties but low fluorescence efficiency. We have found significant increases in the fluorescence efficiency of individual DNA-wrapped SWNTs upon addition of reducing agents, including dithiothreitol, Trolox, and β-mercaptoethanol. Brightening was reversible upon removal of the reducing molecules, suggesting that a transient reduction of defect sites on the SWNT sidewall causes the effect. These results imply that SWNTs are intrinsically bright emitters and that their poor emission arises from defective nanotubes.     

Nano-electromechanical displacement sensing based on single-walled carbon nanotubes

We present a nano-electromechanical system based on an individual single-walled carbon nanotube (SWNT) demonstrating their potential use for future displacement sensing at the nanoscale. The fabrication and characterization of the proposed nanoscaled transducer, consisting of a suspended metal cantilever mounted on top of the center of a suspended SWNT, is presented and discussed. The displacement of the nanoscale cantilever is detected via the electromechanically induced change in conductance of the strained SWNT. A relative differential resistance sensitivity (for a metallic SWNT) of up to 27.5%/nm was measured and a piezoresistive gauge factor of a SWNT of up to 2900 was extracted.     

Structure-dependent fluorescence efficiencies of individual single-walled carbon nanotubes

Single-nanotube photometry was used to measure the product of absorption cross section and fluorescence quantum yield for 12 (n,m) structural species of semiconducting single-walled carbon nanotubes in aqueous SDBS suspension. These products ranged from 1.7 to 4.5 x 10(-19) cm(2)/C atom, generally increasing with optical band gap as described by the energy gap law. The findings suggest fluorescent quantum yields of approximately 8% for the brightest, (10,2) species and introduce the empirical calibration factors needed to deduce quantitative (n,m) distributions from bulk fluorimetric intensities.     

Electrochemical sensing based on redox mediation at carbon nanotubes

An electrochemical sensing platform was developed based on the integration of redox mediators and carbon nanotubes (CNT) in a polymeric matrix. To demonstrate the concept, a redox mediator Azure dye (AZU) was covalently attached to polysaccharide chains of chitosan (CHIT) and interspersed with CNT to form composite films for the amperometric determination of beta-nicotinamide adenine dinucleotide (NADH). The incorporation of CNT into CHIT-AZU matrix facilitated the AZU-mediated electrooxidation of NADH. In particular, CNT decreased the overpotential for the mediated process by an extra 0.30 V and amplified the NADH current by approximately 35 times (at -0.10 V) while reducing the response time from approximately 70 s for CHIT-AZU to approximately 5 s for CHIT-AZU/CNT films. These effects were discussed in terms of the AZU/CNT synergy, which improved charge propagation through the CHIT-AZU/CNT matrix. The concept of CNT-facilitated redox mediation in polymeric matrixes has a potential to be of general interest for expediting redox processes in electrochemical devices such as sensors, biosensors, and biological fuel cells and reactors.     

Vertically aligned multiwalled carbon nanotubes for pressure, tactile and vibration sensing

We report a simple method for the micro-nano integration of flexible, vertically aligned multiwalled CNT arrays sandwiched between a top and bottom carbon layer via a porous alumina (Al(2)O(3)) template approach. The electromechanical properties of the flexible CNT arrays have been investigated under mechanical stress conditions. First experiments show highly sensitive piezoresistive sensors with a resistance decrease of up to ～35% and a spatial resolution of <1?mm. The results indicate that these CNT structures can be utilized for tactile sensing components. They also confirm the feasibility of accessing and utilizing nanoscopic CNT bundles via lithographic processing. The method involves room-temperature processing steps and standard microfabrication techniques.     

Laser-assisted fabrication of biomolecular sensing microarrays

With the aim of obtaining high density biosensing arrays we use pulsed laser deposition to immobilize functional biomolecules on useful surfaces, and micro- and nanopatterning techniques for fabrication of prototype immunosensing bioarrays. We report biological activity tests demonstrating the functional properties of the immobilized proteins and atomic force microscopy characterization of films of nanometric dimensions. Laser-fabricated immunofluorescent arrays are analyzed to check that the intensity and contrast of the sensing sites allow efficient device fabrication. We have also developed an elementary array of heterogeneous reaction sites and tested its performance by simultaneous incubation with the different specific antigens.     

Vapor sensing performances of PVDF nanocomposites containing titanium dioxide nanotubes decorated multi-walled carbon nanotubes

Inorganic nanocarbon hybrid materials are good alternatives for superior electrochemical performance and specific capacitance to their traditional counterparts. Nanocarbons act as a good template for the growth of metal nanoparticles on it and their hybrid combinations enhance the charge transport and rate capability of electrochemical materials without sacrificing the specific capacity. In this study, titanium dioxide nanotubes (TNT) are synthesized hydrothermally in the presence of multi-walled carbon nanotubes (MWCNT) where the latter acts as base template material for the metal oxide nanotube growth. The MWCNT–TNT hybrid material possesses very high dielectric strength and this is used to enhance the dielectric property of the polymer polyvinyledene fluoride (PVDF). Solution mixing was used to prepare the PVDF/MWCNT–TNT nanocomposites by varying the filler concentrations from 0.5 to 2.5 wt%. Excellent vapor sensing was noticed for the PVDF nanocomposites with different rate of response towards commonly used laboratory solvents. The composites and the fillers were characterized for its morphology and structural properties using scanning and transmission electron microscopy, X-ray diffraction studies and infrared spectroscopy. Vapor sensing was measured as relative resistance variations against the solvent vapors, and the dielectric properties of the composites were measured at room temperature during the frequency 10²–10⁷ Hz. Experimental results revealed the influence of filler synergy on the properties of PVDF and the enhancement in the solvent vapor detectability and dielectric properties reflects the ability of these composite films in flexible vapor sensors and in energy storage.     

二氧化锡包覆多壁碳纳米管的室温氢敏性能

采用SnCl2溶液法制备二氧化锡包覆多壁碳纳米管(SnO2coated multi-wall carbon nanotubes,SnO2/MWCNTs),研究了SnO2/MWCNTs的室温氢敏性能。SEM和TEM形貌观察表明:粒径5nm的SnO2均匀包覆在MWCNTs表面,并形成连续的包覆层。氢敏性能测试表明:SnO2/MWCNTs材料具有室温氢敏性能,可以实现体积浓度0.01%氢气的检测。在对0.1%氢/氩混合气的室温氢敏测试中发现,当通入空气后出现电流反向波动的现象,这是由于空气中的O2与样品周围的H2生成H2O并吸附在SnO2表面,降低了SnO2/MWCNTs的电阻,随后由于O的竞争吸附,HO又脱附所导致。这一电流反向波动现象暗示SnO/MWCNTs具有室温湿敏性能。